Silicon-containing underlayers

ABSTRACT

Methods of manufacturing electronic devices employing wet-strippable underlayer compositions comprising a condensate and/or hydrolyzate of a polymer comprising as polymerized units one or more first unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the polymer backbone, and one or more condensable silicon monomers are provided.

This application is a continuation of U.S. application Ser. No.16/133,739, filed Sep. 18, 2018, which claims the benefit of priorityunder 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/584,151,filed Nov. 10, 2017.

The present invention relates generally to underlayers and methods ofusing them, and particularly to wet-strippable silicon-containingunderlayers and their use in the manufacture of electronic devices.

In conventional photolithographic processes, the resist pattern is usedas a mask for pattern transfer to the substrate by suitable etchingprocesses, such as by reactive ion etch (RIE). The continued decrease inthe thickness of the resist used makes the resist pattern unsuitable asa mask for pattern transfer by RIE processes. As a result, alternateprocesses have been developed using three, four or more layers as a maskfor pattern transfer. For example, in a trilayer process asilicon-containing antireflective layer is disposed between anunderlayer/organic planarizing layer and the resist layer. Due to thealternating selectivity towards fluorine and oxygen-containing RIEchemistry these layers possess, this trilayer scheme provides highlyselective pattern transfer from the resist pattern on top of theSi-containing layer into the substrate below the underlayer.

The resistance of the silicon-containing underlayer toward oxide-etchchemistry allows this layer to function as an etch mask. Suchsilicon-containing underlayers are comprised of a crosslinked siloxanenetwork. The etch resistance of these materials results from the siliconcontent, with a higher silicon content providing better etch resistance.In current 193 nm lithographic processes, such silicon-containingunderlayers contain ≥30% silicon. Such high silicon content and siloxanenetwork structure in these materials makes their removal challenging.Fluorine-containing plasma and hydrofluoric acid (HF) can both be usedto remove (or strip) these silicon-containing layers. However, bothF-plasma and HF will remove not only these silicon-containing materialsbut also other materials that are desired to remain, such as thesubstrate. Wet stripping using tetramethylammonium hydroxide (TMAH) inhigher concentrations, such as ≥5 wt %, can be used to remove at leastsome of these silicon-containing layers, but these higher concentrationsof TMAH also risk damaging the substrate. Silicon-containing layershaving a relatively lower amount of silicon (≤17%) can sometimes beremoved using “piranha acid” (concentrated H₂SO₄+30% H₂O₂), but such anapproach has not achieved commercial success with silicon-containingmaterials having higher silicon content.

Cao et al., Langmuir, 2008, 24, 12771-12778, have reported microgelsformed by free radical copolymerization of N-isopropyl acrylamide and3-(trimethoxysilyl)propyl methacrylate, followed by cross-linking viahydrolysis and condensation of the methoxysilyl groups. Cao et al.describe such materials as being useful in biological applications, suchas controlled drug release materials, biosensors and in tissueengineering. U.S. Pat. No. 9,120,952 employs materials similar to thosedisclosed in the Cao et al. reference for use in chemical mechanicalplanarization processing.

U.S. Pat. No. 8,932,953 B2 discloses compositions for forming asilicon-containing resist underlayer, wherein the compositions contain acombination of component (i) and component (ii). In this patent,component (i) is a polymer having repeating units of formula (A) andformula (B) and being capable of generating a phenolic hydroxyl group,and component (ii) is a silicon-containing compound obtained byhydrolysis-condensation of a mixture containing at least one or morehydrolysable compounds of formula (C) and one or more hydrolysablecompounds of formula (D).

That is, the compositions in U.S. Pat. No. 8,932,953 are a combinationof (i) certain organic polymers having both pendent aryl moieties andpendent Si—O linkages and (ii) certain siloxane polymers, wherein thependent aryl moieties are capable of generating a phenolic hydroxylgroup. This combination of components (i) and (ii) is required in U.S.Pat. No. 8,932,953 in order to achieve a composition capable of forminga resist underlayer film not only having excellent storage stability andadhesion but also having patterning properties unchanged in a positivedevelopment and in a negative development. Films formed from thecompositions of this patent are removed by etching processes.

Recent advances in the field of underlayers have provided certainsilicon-containing materials that can be readily removed by wetstripping techniques. One drawback is that underlayers of suchsilicon-containing materials tend to suffer from dissolution or swellingupon exposure to developers such as tetramethylammonim hydroxide (TMAH)which can lead to collapse of photoresist patterns formed on theseunderlayers. There remains a need for silicon-containing underlayersthat can be removed by wet stripping and that are more resistant tophotoresist pattern collapse.

The present invention provides a composition comprising: (a) one or moresolvents; (b) a condensate and/or hydrolyzate of (i) one or morecondensed silicon-containing polymers comprising as polymerized unitsone or more first unsaturated monomers having a condensablesilicon-containing moiety, wherein the condensable silicon-containingmoiety is pendent to the polymer backbone, and (ii) one or morecondensable silicon monomers; and (c) one or more crosslinkers free ofSi—O linkages. The one or more crosslinkers are capable of reacting toform covalent bonds with the one or more silicon-containing polymers.

Also provided by the present invention is a composition comprising: (a)one or more solvents; (b) one or more condensed polymers having anorganic polymer chain having pendently-bound siloxane moieties; and (c)one or more crosslinkers free of Si—O linkages.

The present invention further provides a method comprising (a) coating asubstrate with any of the compositions described above, to form acoating layer; (b) curing the coating layer to form a polymericunderlayer; (c) disposing a layer of a photoresist on the polymericunderlayer; (d) pattern-wise exposing the photoresist layer to form alatent image; (e) developing the latent image to form a patternedphotoresist layer having a relief image therein; (f) transferring therelief image to the substrate; and (g) removing the polymeric underlayerby wet stripping. The present polymeric underlayer is a cured coatingcomprising as polymerized units one or more condensed polymers havingpendent siloxane moieties and one or more crosslinkers free of Si—Olinkages.

Still further, the present invention provides a coated substrate havinga cured coating layer comprising as polymerized units: (a) one or morecondensates and/or hydrolyzates of (i) one or more polymers comprisingas polymerized units one or more first unsaturated monomers having acondensable silicon-containing moiety, wherein the condensablesilicon-containing moiety is pendent to the polymer backbone, and (ii)one or more condensable silicon monomers; and (b) one or morecrosslinkers free of Si—O linkages. Alternatively, the present inventionprovides a coated substrate having a cured coating layer comprising aspolymerized units: (a) one or more condensed polymers having an organicpolymer chain having pendently-bound siloxane moieties; and (b) one ormore crosslinkers free of Si—O linkages.

It will be understood that when an element is referred to as being“adjacent” to or “on” another element, it can be directly adjacent to oron the other element or intervening elements may be presenttherebetween. In contrast, when an element is referred to as being“directly adjacent” or “directly on” another element, there are nointervening elements present. It will be understood that although theterms first, second, third, etc. may be used to describe variouselements, components, regions, layers and/or sections, these elements,components, regions, layers and/or sections should not be limited bythese terms. These terms are only used to distinguish one element,component, region, layer or section from another element, component,region, layer or section. Thus, a first element, component, region,layer or section discussed below could be termed a second element,component, region, layer or section without departing from the teachingsof the present invention.

As used throughout this specification, the following abbreviations shallhave the following meanings, unless the context clearly indicatesotherwise: ° C.=degree Celsius; g=gram; mg=milligram; ppm=part permillion by weight unless otherwise noted; μm=micron=micrometer;nm=nanometer; A=angstrom; L=liter; mL=milliliter; sec.=second;min.=minute; hr.=hour; and Da=Dalton. All amounts are percent by weightand all ratios are molar ratios, unless otherwise noted. All numericalranges are inclusive and combinable in any order, except where it isclear that such numerical ranges are constrained to add up to 100%. “Wt%” refers to percent by weight, based on the total weight of areferenced composition, unless otherwise noted. The articles “a”, “an”and “the” refer to the singular and the plural. As used herein, the term“and/or” includes any and all combinations of one or more of theassociated listed items. M_(w) refers to weight average molecular weightand is determined by gel permeation chromatography (GPC) usingpolystyrene standards. Reported pKa values are for aqueous solutions at25° C. which may be determined experimentally, for example, bypotentiometric titration such as by using a potentiometric pH meteravailable from Sirius Analytical Instruments Ltd., or may be calculated,for example, by using Advanced Chemistry Development (ACD) Labs SoftwareVersion 11.02. Unless otherwise noted, all measurements reported hereinare made at room temperature.

As used throughout the specification, the term “alkyl” includes linear,branched and cyclic alkyl. The term “alkyl” refers to an alkane radical,and includes alkane monoradicals, diradicals (alkylene), andhigher-radicals. If no number of carbons is indicated for any alkyl orheteroalkyl, then 1-12 carbons are contemplated. The term “heteroalkyl”refers to an alkyl group with one or more heteroatoms, such as nitrogen,oxygen, sulfur, phosphorus, replacing one or more carbon atoms withinthe radical, for example, as in an ether or a thioether. The term“alkenyl” refers to an alkene radical, and includes alkene monoradicals,diradicals (alkenylene), and higher-radicals. “Alkenyl” refers tolinear, branched and cyclic alkene radicals unless otherwise specified.The term “alkynyl” refers to an alkyne radical, and includes alkynemonoradicals, diradicals, and higher-radicals. “Alkynyl” refers tolinear and branched alkyne radicals. If no number of carbons isindicated for any alkenyl or alkynyl, then 2-12 carbons arecontemplated. “Organic residue” refers to the radical of any organicmoiety, which may optionally contain one or more heteroatoms, such asoxygen, nitrogen, silicon, phosphorus, and halogen, in addition tocarbon and hydrogen. An organic residue may contain one or more aryl ornon-aryl rings or both aryl and non-aryl rings. The term “hydrocarbyl”refers to a radical of any hydrocarbon, which may be aliphatic, cyclic,aromatic or a combination thereof, and which may optionally contain oneor more heteroatoms, such as oxygen, nitrogen, silicon, phosphorus, andhalogen, in addition to carbon and hydrogen. The hydrocarbyl moietiesmay contain aryl or non-aryl rings or both aryl and non-aryl rings, suchas one or more alicyclic rings, or aromatic rings or both alicyclic andaromatic rings. When a hydrocarbyl moiety contains two or more alicyclicrings, such alicyclic rings may be isolated, fused or spirocyclic.Alicyclic hydrocarbyl moieties include single alicyclic rings, such ascyclopentyl and cyclohexyl, as well as bicyclic rings, such asdicyclopentadienyl, norbornyl, and norbornenyl. When the hydrocarbylmoiety contains two or more aromatic rings, such rings may be isolatedor fused. By the term “curing” is meant any process, such aspolymerization or condensation, that increases the molecular weight of amaterial or composition. “Curable” refers to any material capable ofbeing cured under certain conditions. The term “oligomer” refers todimers, trimers, tetramers and other relatively low molecular weightmaterials that are capable of further curing. The term “polymer”includes oligomers and refers to homopolymers, copolymers, terpolymers,tetrapolymers and the like. As used herein, the terms “(meth)acrylate”and “(meth)acrylic acid” refer to both acrylate and methacrylate, andacrylic acid and methacrylic acid, respectively.

Compositions useful in the present invention comprise a condensedsilicon-containing polymer (also referred to herein as a “condensedpolymer”). Coatings of the present compositions, and films andunderlayers formed therefrom, are wet strippable, and have reducedpattern collapse as compared to conventional wet-strippablesilicon-containing underlayers. As used herein, the term “condensedpolymer” refers to a condensate and/or hydrolyzate of (i) one or morepolymers comprising as polymerized units one or more first unsaturatedmonomers having a condensable silicon-containing moiety, wherein thecondensable silicon-containing moiety is pendent to the polymerbackbone, and (ii) one or more condensable silicon monomers, oralternatively, a polymer having an organic polymer chain havingpendently-bound siloxane moieties. As used herein, the term “condensateand/or hydrolyzate” refers to a condensation product, a hydrolysisproduct, a hydrolysis-condensation product, or a combination of any ofthe foregoing. The term “hydrolysis product” refers to both a product ofpartial hydrolysis or complete hydrolysis.

The present condensed polymers have an organic polymer chain (orbackbone) having pendently-bound siloxane moieties. The organic polymerchain comprises as polymerized units, preferably free-radicallypolymerized units, one or more first unsaturated monomers having acondensable silicon-containing moiety. Upon polymerization, preferablyfree-radical polymerization, of the one or more first unsaturatedmonomers and any optional second unsaturated monomers, the resultingorganic polymer chain has one or more pendent condensablesilicon-containing moieties. The one or more pendent condensablesilicon-containing moieties of the organic polymer chain are thencondensed and/or hydrolyzed with one or more condensable siliconmonomers to form the present condensed polymers having pendently-boundsiloxane moieties. As used herein, the term “siloxane moieties” refersto moieties having at least one (Si—O) unit. The condensed polymers ofthe invention may optionally, and preferably do, have a polymer chaincomprising as polymerized units one or more second unsaturated monomers.Preferably, each of the first unsaturated monomers and any secondunsaturated monomers comprise one radical polymerizable double or triplebond, more preferably a radical polymerizable carbon-carbon double ortriple bond, and even more preferably one radical polymerizablecarbon-carbon double bond. The present condensed polymers are preferablyfree of repeating units of a monomer having two or more radicalpolymerizable double bonds.

Any unsaturated monomer having a condensable silicon-containing moietyis suitable for use as the first unsaturated monomer to form the presentcondensed polymers. One or more first unsaturated monomers may be used.Ethylenically unsaturated monomers having a condensablesilicon-containing moiety are preferred. Preferred first unsaturatedmonomers are those having a condensable silicon-containing moiety of theformula (1)*-L-SiR¹ _(b)Y¹ _(3-b)  (1)wherein L is a single bond or a divalent linking group; each R¹ isindependently chosen from H, C₁₋₁₀-alkyl, C₂₋₂₀-alkenyl, C₅₋₂₀-aryl, andC₆₋₂₀-aralkyl; each Y¹ is independently chosen from halogen,C₁₋₁₀-alkoxy, C₅₋₁₀-aryloxy, and C₁₋₁₀-carboxy; b is an integer from 0to 2; and * denotes the point of attachment to the monomer. It ispreferred that L is a divalent linking group. It is further preferredthat the divalent linking group comprises one or more heteroatoms chosenfrom oxygen and silicon. A suitable divalent linking group is an organicradical having from 1 to 20 carbon atoms and optionally one or moreheteroatoms. Preferred divalent linking groups have the formulaC(═O)—O-L¹- wherein L¹ is a single bond or an organic radical havingfrom 1 to 20 carbon atoms. Preferably, each R¹ is independently chosenfrom C₁₋₁₀-alkyl, C₂₋₂₀-alkenyl, C₅₋₂₀-aryl, and C₆₋₂₀-aralkyl. It ispreferred that each Y¹ is independently chosen from halogen,C₁₋₆-alkoxy, C₅₋₁₀-aryloxy, C₁₋₆-carboxy, and more preferably fromhalogen, C₁₋₆-alkoxy, and C₁₋₆-carboxy. Preferably, b is 0 or 1, andmore preferably b=0.

It is preferred that at least one first unsaturated monomer has theformula (2)

wherein L is a single bond or a divalent linking group; each R¹ isindependently chosen from H, C₁₋₁₀-alkyl, C₂₋₂₀-alkenyl, C₅₋₂₀-aryl, andC₆₋₂₀-aralkyl; each of R² and R³ are independently chosen from H,C₁₋₄-haloalkyl, halogen, C₅₋₂₀-aryl, C₆₋₂₀-aralkyl, and CN; R⁴ is chosenfrom H, C₁₋₁₀-alkyl, C₁₋₁₀-haloalkyl, halogen, C₅₋₂₀-aryl,C₆₋₂₀-aralkyl, and C(═O)R⁵; R⁵ is chosen from OR⁶ and N(R⁷)₂; R⁶ ischosen from H, C₁₋₂₀ alkyl, C₅₋₂₀-aryl, and C₆₋₂₀-aralkyl; each R⁷ isindependently chosen from H, C₁₋₂₀-alkyl, and C₅₋₂₀-aryl; each Y¹ isindependently chosen from halogen, C₁₋₁₀-alkoxy, C₅₋₁₀-aryloxy,C₁₋₁₀-carboxy; and b is an integer from 0 to 2. It is preferred that Lis a divalent linking group. It is further preferred that the divalentlinking group comprises one or more heteroatoms chosen from oxygen andsilicon. A suitable divalent linking group is an organic radical havingfrom 1 to 20 carbon atoms and optionally one or more heteroatoms.Preferred divalent linking groups have the formula C(═O)—O-L¹- whereinL¹ is a single bond or an organic radical having from 1 to 20 carbonatoms. Preferably, each R¹ is independently chosen from C₁₋₁₀-alkyl,C₂₋₂₀-alkenyl, C₅₋₂₀-aryl, and C₆₋₂₀-aralkyl. It is preferred that eachY¹ is independently chosen from halogen, C₁₋₆-alkoxy, C₅₋₁₀-aryloxy,C₁₋₆-carboxy, and more preferably from halogen, C₁₋₆-alkoxy, andC₁₋₆-carboxy. Preferably, b is 0 or 1, and more preferably b=0. It ispreferred that each R² and R³ are independently chosen from H,C₁₋₄-alkyl, C₁₋₄-haloalkyl, C₅₋₂₀-aryl, and C₆₋₂₀-aralkyl, and morepreferably from H, C₁₋₄-alkyl, C₅₋₂₀-aryl, and C₆₋₂₀-aralkyl. Yet morepreferably, each R² and R³ are independently chosen from H, methyl,ethyl, propyl, butyl, phenyl, naphthyl, benzyl, and phenethyl. R⁴ ispreferably chosen from H, C₁₋₁₀-alkyl, C₁₋₁₀-haloalkyl, C₅₋₂₀-aryl,C₆₋₂₀-aralkyl, and C(═O)R⁵, and more preferably from H, C₁₋₁₀-alkyl,C₅₋₂₀-aryl, C₆₋₂₀-aralkyl, and C(═O)R⁵. It is preferred that R⁵ is OR⁶.R⁶ is preferably chosen from H, C₁₋₁₀-alkyl, C₅₋₁₀-aryl, andC₆₋₁₅-aralkyl. Preferably, each 127 is independently chosen from H,C₁₋₁₀-alkyl, and C₆₋₂₀-aryl.

Suitable first unsaturated monomers having a condensablesilicon-containing moiety are generally commercially available from avariety of sources, such as Sigma-Aldrich (St. Louis, Mo.), or may beprepared by methods known in the art. Such monomers may be used as-is,or may be further purified. Exemplary first unsaturated monomersinclude, but are not limited to: allyl dimethoxysilane; allyldichlorosilane; (trimethoxysilyl)methyl (meth)acrylate;(trimethoxysilyl)ethyl (meth)acrylate; (trimethoxysilyl)propyl(meth)acrylate; (trimethoxysilyl)butyl (meth)acrylate;(triethoxysilyl)methyl (meth)acrylate; (triethoxysilyl)ethyl(meth)acrylate; (triethoxysilyl)propyl (meth)acrylate;(triethoxysilyl)butyl (meth)acrylate; (trichlorosilyl)methyl(meth)acrylate; (trichlorosilyl)ethyl (meth)acrylate;(trichlorosilyl)propyl (meth)acrylate; (trichlorosilysilyl)butyl(meth)acrylate; (methyldimethoxysilyl)propyl (meth)acrylate;vinyltriacetoxysilane; (triacetoxysilyl)propyl (meth)acrylate;4-((trimethoxysilyl)propyl)styrene; 4-(trimethoxysilyl)styrene; andvinyltrimethoxysilane.

Preferably, the organic polymer chain of the present condensed polymersfurther comprises as polymerized units one or more second unsaturatedmonomers, where such second monomers are free of a condensablesilicon-containing moiety. Preferred second unsaturated monomers areethylenically unsaturated monomers. Preferably, the condensed polymershave an organic polymer chain further comprising as polymerized unitsone or more second unsaturated monomers of formula (3)

wherein Z is chosen from an organic residue having from 1 to 30 carbonatoms and an acidic proton having a pKa in water from −5 to 13, anorganic residue having from 1 to 30 carbon atoms and an aciddecomposable group, an organic residue having a chromophore moiety,—C(═O)R¹³ and CN; each of R¹⁰, R¹¹ and R¹² is independently chosen fromH, C₁₋₄-alkyl, C₁₋₄-haloalkyl, optionally substituted C₅₋₂₀-aryl,halogen, —C(═O)R¹⁴, C₆₋₁₀-aryl, and CN; each of R¹³ and R¹⁴ isindependently OR¹⁵ or N(R¹⁶)₂; R¹⁵ is chosen from H, C₁₋₂₀-alkyl,optionally substituted C₅₋₃₀-aryl, C₆₋₂₀-aralkyl and a monovalentorganic residue having a lactone moiety; and each R¹⁶ is independentlychosen from H, C₁₋₂₀-alkyl, and C₆₋₂₀-aryl; wherein Z and R¹⁰ may betaken together to form a 5 to 7-membered unsaturated ring. Preferably, Zis chosen from an organic residue having from 1 to 30 carbon atoms andan acidic proton having a pKa in water from −5 to 13, an organic residuehaving from 1 to 30 carbon atoms and an acid decomposable group, anorganic residue having from 5 to 40 carbon atoms and having achromophore moiety, and —C(═O)R¹³. A preferred halogen is fluorine. Itis preferred that each of R¹⁰, R¹¹ and R¹² is independently chosen fromH, C₁₋₄-alkyl, C₁₋₄-haloalkyl, halogen, —C(═O)R¹⁴, and C₆₋₁₀-aryl, andmore preferably from H, methyl, trifluoromethyl, fluorine, and—C(═O)R¹⁴. Preferably, each of R¹³ and R¹⁴ is OR¹⁵. R¹⁵ is preferablychosen from H, C₁₋₂₀-alkyl, C₆₋₂₀-aryl, C₆₋₂₀-aralkyl and a monovalentorganic residue having a lactone moiety. As used herein, the term “aryl”refers to aromatic carbocycles and aromatic heterocycles. “Optionallysubstituted” aryl refers to both unsubstituted and substituted aryl.“Substituted aryl” refers to any aryl (or aromatic) moiety having one ormore of its hydrogens replaced with one or more substituents chosen fromhalogen, C₁₋₆-alkyl, C₁₋₆-haloalkyl, C₁₋₆-alkoxy, C₁₋₆-haloalkoxy,phenyl, and phenoxy, preferably from halogen, C₁₋₆-alkyl, C₁₋₆-alkoxy,phenyl, and phenoxy, and more preferably from halogen, C₁₋₆-alkyl, andphenyl. Preferably, a substituted aryl has from 1 to 3 substituents, andmore preferably 1 or 2 substituents. It is preferred that the presentcondensed polymers have an organic polymer chain further comprising aspolymerized units two or more different second unsaturated monomers offormula (4). The mole ratio of the total moles of the first unsaturatedmonomers of formula (1)+formula (2) to the total moles of any optionalsecond unsaturated monomers such as those of formula (3) is from 100:0to 25:75, preferably from 95:5 to 25:75, and more preferably from 75:25to 25:75.

Preferred monomers of formula (3) wherein Z is an organic residue havingfrom 1 to 30 carbon atoms and an acidic proton having a pKa in waterfrom −5 to 13 are those of formula (3a)

wherein L¹ is a single bond or a divalent linking group; AM is an acidicmoiety having an acidic proton and having a pKa in water from −5 to 13;each of R^(10a), R^(11a) and R^(12a) is independently chosen from H,C₁₋₄-alkyl, C₁₋₄-haloalkyl, optionally substituted C₆₋₂₀-aryl, halogen,—C(═O)R^(14a), and CN; R^(14a) is chosen from OR^(15a) and N(R^(16a))₂,R^(15a) is chosen from H, C₁₋₂₀-alkyl, C₅₋₃₀-aryl, C₆₋₂₀-aralkyl and amonovalent organic residue having a lactone moiety; and each R^(16a) isindependently chosen from H, C₁₋₂₀-alkyl, and C₆₋₂₀-aryl; wherein anytwo of L¹, R^(10a), R^(11a), and R^(12a) may be taken together with thecarbons to which they are attached to form a 5 to 7-membered ring.Preferably, each of R^(11a) and R^(12a) is independently chosen from H,C₁₋₄-alkyl, C₁₋₄-haloalkyl, optionally substituted C₆₋₂₀-aryl, andhalogen, and more preferably from H, C₁₋₄-alkyl, C₁₋₄-haloalkyl, andoptionally substituted C₆₋₁₀-aryl. A preferred halogen is fluorine. Itis preferred that R^(10a) is chosen from H, C₁₋₁₀-alkyl,C₁₋₁₀-haloalkyl, optionally substituted C₆₋₂₀-aryl, and —C(═O)R^(14a),and more preferably from H, C₁₋₁₀-alkyl, C₁₋₁₀-haloalkyl, optionallysubstituted C₆₋₁₀-aryl, and —C(═O)R^(14a). R^(14a) is preferablyOR^(15a). It is preferred that R^(15a) is H, C₁₋₂₀-alkyl, C₅₋₃₀-aryl,and C₆₋₂₀-aralkyl, and more preferably H. Each R^(16a) is preferablychosen from H, and C₁₋₂₀-alkyl. L¹ is preferably a single covalent bondor a divalent organic radical having from 1 to 20 carbon atoms andoptionally one or more heteroatoms, more preferably L¹ is a singlecovalent bond or a divalent hydrocarbyl radical having from 1 to 20carbon atoms and optionally one or more oxygen atoms, and still morepreferably L¹ is chosen from a single covalent bond, a divalentC₁₋₂₀-aliphatic moiety optionally comprising one or more oxygen atoms, adivalent optionally substituted C₆₋₂₀-aryl moiety, and a divalentoptionally substituted C₇₋₂₀-alkylaryl moiety. Suitable acidic moietiesfor AM have one or more acidic groups chosen from carboxylic acid,sulfonic acid, sulfinic acid, sulfamic acid, phosphonic acid, boronicacid, aromatic hydroxyl, hydroxy-hexafluoroisopropyl, and combinationsand acid salts thereof, preferably from carboxylic acid, sulfonic acid,phosphonic acid, boronic acid, and combinations and acid salts thereof,more preferably from carboxylic acid, sulfonic acid, phosphonic acid,boronic acid, and combinations thereof, and still more preferablycarboxylic acid. Yet more preferably, AM is chosen from —C(═O)—OH,—S(═O)₂—OH, —P(═O)(OH)₂, —B(OH)₂, C₆₋₂₀-hydroxyaryl, mercapto, andC₁₋₁₂-hydroxy-perfluoroalkyl, and more preferably from —C(═O)—OH,—S(═O)₂—OH, —P(═O)(OH)₂, —B(OH)₂, C₆₋₂₀-hydroxyaryl, mercapto, andC₁₋₆-hydroxy-perfluoroalkyl such as hexafluoro-iso-propanoyl, and morepreferably AM is —C(═O)—OH. L¹ and R^(10a) or R^(11a) and R^(12a) may betaken together along with the carbons to which they are attached to forma 5- to 7-membered unsaturated ring, preferably a 5- to 6-memberedunsaturated ring, and more preferably a 5- to 6-membered unsaturatedcarbocyclic ring. R^(10a) and R^(11a) or R^(12a) and L¹ may be takentogether along with the carbons to which they are attached to form a 5-to 7-membered saturated or unsaturated ring, preferably a 5- to6-membered saturated or unsaturated ring, and more preferably a 5- to6-membered saturated or unsaturated carbocyclic ring.

Other preferred second unsaturated monomers of formula (3) are those offormula (4)

wherein ADG is an acid decomposable group; and R²⁰ is chosen from H,C₁₋₄-alkyl, C₁₋₄-haloalkyl, halogen, and CN. R²⁰ is preferably chosenfrom H, C₁₋₄-fluoroalkyl, fluorine, and CN, more preferably from H,C₁₋₄-alkyl, trifluoromethyl, fluorine, and CN, even more preferably fromH, methyl, trifluoromethyl, fluorine, and CN, and most preferably R²⁰ isH or methyl. In formula (4), ADG is an acid decomposable group havingfrom 2 to 30 carbon atoms. The term “acid decomposable group”, as usedherein, refers to any functional group capable of being decomposed byacid to form a different functional group having increased aqueous basesolubility as compared to the acid decomposable group. Suitable aciddecomposable groups include, but are not limited to,—O—C₄₋₃₀-hydrocarbyl moiety where the C₄₋₃₀-hydrocarbyl moiety is bondedto the oxygen atom through a tertiary carbon atom, a C₂₋₃₀-hydrocarbylmoiety having an anhydride moiety, a C₂₋₃₀-hydrocarbyl moiety having animide moiety, and a C₄₋₃₀-organic residue comprising an acetalfunctional group. Preferred acid decomposable groups are—O—C₄₋₃₀-hydrocarbyl moiety where the C₄₋₃₀-hydrocarbyl moiety is bondedto the oxygen atom through a tertiary carbon atom, and a C₄₋₃₀-organicresidue comprising an acetal functional group, and more preferably—O—C₄₋₃₀-hydrocarbyl moiety where the C₄₋₂₀-hydrocarbyl moiety is bondedto the oxygen atom through a tertiary carbon atom, and a C₄₋₂₀-organicresidue comprising an acetal functional group. As used herein, the term“acetal” also embraces “ketal”, “hemiacetal”, and “hemiketal.” Exemplaryacid decomposable groups include, without limitation, —NR²¹R²², —OR²³,and —O—C(═O)—R²⁴ wherein R²¹ and R²² are each independently chosen fromH, C₁₋₂₀-alkyl, and C₅₋₁₀-aryl; R²³ is a C₄₋₃₀-organic residue bound tothe oxygen through a tertiary carbon (that is, a carbon that is bound tothree other carbons, respectively) or a C₄₋₃₀-organic residue comprisingan acetal functional group; and R²⁴ is chosen from H, C₁₋₃₀-alkyl, andC₅₋₃₀-aryl. Preferably, R²³ has from 4 to 20 carbon atoms. It is furtherpreferred that R²³ is a branched or cyclic moiety. When R²³ contains acyclic moiety, such cyclic moiety typically has from 4 to 8 atoms in thering, and preferably 5 or 6 atoms in the ring. R²³ may optionallycontain one or more heteroatoms such as oxygen. Preferably, R²³ is abranched aliphatic or a cycloaliphatic moiety optionally containing oneor more heteroatoms.

Preferred second unsaturated monomers of formula (4) are those offormula (4a)

wherein R²³ is chosen from a C₄₋₂₀-organic residue bound to the oxygenthrough a tertiary carbon or a C₄₋₂₀-organic residue comprising anacetal functional group; and R²⁰ is chosen from H, C₁₋₄-alkyl,C₁₋₄-haloalkyl, halogen, and CN. More preferably, R²³ has the structureshown in formula (5a) or (5b)

wherein each of R²⁴, R²⁵ and R²⁶ is independently an organic residuehaving from 1 to 6 carbon atoms; R²⁴ and R²⁵ may be taken together toform a 4 to 8 membered ring; L² is a divalent linking group or a singlechemical bond; A represents an acetal functional group; and * indicatesthe point of attachment to the ester oxygen. It is preferred that eachof R²⁴, R²⁵ and R²⁶ is independently chosen from C₁₋₆-alkyl. When R²⁴and R²⁵ are taken together to form a 4 to 8 membered ring, such ring maybe a single ring or may be bicyclic, and may optionally contain one ormore heteroatoms chosen from oxygen, sulfur and nitrogen, preferablyoxygen and sulfur and more preferably oxygen. Preferably, R²⁴ and R²⁵may be taken together to form a 5 to 8 membered ring. Suitable 4 to 8membered rings include, but are not limited to, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, norbornyl, and oxabicylco[2.2.1]heptyl,preferably cyclopentyl, cyclohexyl, norbornyl, andoxabicylco[2.2.1]heptyl, and more preferably cyclopentyl and cyclohexyl.Suitable divalent linking groups include C₁₋₁₀-alkylene, and preferablyC₁₋₅-alkylene. Preferably, the acetal functional group is a 5 or6-membered ring cyclic ketal, and more preferably a cyclic ketal formedfrom acetone. Exemplary moieties for R²³ include, without limitation:tert-butyl; 2,3-dimethyl-2-butyl; 2,3,3-trimethyl-2-butyl;2-methyl-2-butyl; 2-methyl-2-pentyl; 3-methyl-3-pentyl;2,3,4-trimethyl-3-pentyl; 2,2,3,4,4-pentamethyl-3-pentyl;1-methyl-1-cyclopentyl; 1-ethyl-1-cyclopentyl;1,2-dimethyl-1-cyclopentyl; 1,2,5-trimethyl-1-cyclopentyl;1,2,2-trimethyl-cyclopentyl; 1,2,2,5-tetramethyl-1-cyclopentyl;1,2,2,5,5-pentamethyl-1-cyclopentyl; 1-methyl-1-cyclohexyl;1-ethyl-1-cyclohexyl; 1,2-dimethyl-1-cyclohexyl;1,2,6-trimethyl-1-cyclohexyl; 1,2,2,6-tetramethyl-1-cyclohexyl;1,2,2,6,6-pentamethyl-1-cyclohexyl; 2,4,6-trimethyl-4-heptyl;3-methyl-3-norbornyl; 3-ethyl-3-norbornyl;6-methyl-2-oxabicylco[2.2.1]hept-6-yl; and2-methyl-7-oxabicylco[2.2.1]hept-2-yl. Preferably, R⁵ is chosen fromtert-butyl; 2,3-dimethyl-2-butyl; 2,3,3-trimethyl-2-butyl;2-methyl-2-butyl; 2-methyl-2-pentyl; 3-methyl-3-pentyl;2,3,4-trimethyl-3-pentyl; 2,2,3,4,4-pentamethyl-3-pentyl;1-methyl-1-cyclopentyl; 1-ethyl-1-cyclopentyl;1,2-dimethyl-1-cyclopentyl; 1,2,5-trimethyl-1-cyclopentyl;1,2,2-trimethyl-cyclopentyl; 1,2,2,5-tetramethyl-1-cyclopentyl;1,2,2,5,5-pentamethyl-1-cyclopentyl; 1-methyl-1-cyclohexyl;1-ethyl-1-cyclohexyl; 1,2-dimethyl-1-cyclohexyl;1,2,6-trimethyl-1-cyclohexyl; 1,2,2,6-tetramethyl-1-cyclohexyl;1,2,2,6,6-pentamethyl-1-cyclohexyl; and 2,4,6-trimethyl-4-heptyl. L2 ispreferably a divalent linking group. Suitable divalent linking groupsfor L2 have are organic residues having from 1 to 20 atoms, and morepreferably from 1 to 20 carbon atoms. Optionally, the divalent linkinggroups of L2 may contain one or more heteroatoms, such as oxygen,nitrogen or a combination thereof. Suitable monomers of formulae (3),(4) and (4a) may be available commercially or made by a variety ofmethods known in the art, such as is disclosed in U.S. Pat. Nos.6,136,501; 6,379,861; and 6,855,475.

Other preferred monomers of formula (3) are those of formula (6)

wherein R^(20a) is independently chosen from H, C₁₋₄-haloalkyl, halogen,and CN; and R³⁰ is a monovalent organic residue having a lactone moiety.In formula (6), R³⁰ is a C₄₋₂₀-monovalent organic residue comprising alactone moiety. R³⁰ may comprise any suitable lactone moiety, andpreferably comprises a 5 to 7-membered lactone, which may be optionallysubstituted. Suitable substituents on the lactone ring are C₁₋₁₀-alkylmoieties. Suitable lactone moieties for R³⁰ are those having formula (7)

wherein E is a 5 to 7-membered ring lactone; each R³¹ is independentlychosen from C₁₋₁₀-alkyl; r is an integer from 0 to 3; Y is a chemicalbond or a divalent linking residue having from 1 to 10 carbon atoms;and * indicates the point of attachment to the oxygen atom of the ester.It is preferred that each R³¹ is independently chosen from C₁₋₆-alkyl,and more preferably C₁₋₄-alkyl. Examples of R³¹ are methyl, ethyl,n-propyl, iso-propyl, n-butyl, sec-butyl, and iso-butyl. Preferably, r=0or 1. Suitable divalent linking residues for Y include, but are notlimited to, divalent organic residues having from 1 to 20 carbon atoms.Suitable divalent organic residues for Y include, without limitation,C₁₋₂₀-hydrocarbyl moieties, C₁₋₂₀-heteroatom-containing hydrocarbylmoieties, and substituted C₁₋₂₀-hydrocarbyl moieties. The term“C₁₋₂₀-heteroatom-containing hydrocarbyl moieties” refers to hydrocarbylmoieties having one or more heteroatoms, such as nitrogen, oxygen,sulfur, phosphorus, within the hydrocarbyl chain. Exemplary heteroatomsinclude, but are not limited to, —O—, —S—, —N(H)—,—N(C₁₋₂₀-hydrocarbyl)-, —C(═O)—O—, —S(═O)—, —S(═O)₂—, —C(═O)—NH—, andthe like. “Substituted C₁₋₂₀-hydrocarbyl moieties” refers to anyhydrocarbyl moiety having one or more hydrogens replaced with one ormore substituents such as halogen, cyano, hydroxy, amino, mercapto, andthe like. It is preferred that R³⁰ is chosen from gamma-butyrolactone(GBLO), beta-butyrolactone, gamma-valerolactone, delta-valerolactone,and caprolactone, and more preferably, R³⁰ is GBLO. Monomers of formula(6) are generally commercially available or may be prepared by methodsknown in the art.

In one preferred embodiment, the present condensed polymers have apolymer chain that further comprise as polymerized units, one or moresecond unsaturated monomers comprising a chromophore. Suitablechromophores are any aromatic (aryl) moiety that absorbs radiation atthe wavelength of interest. Such chromophores are unsubstituted aromaticmoieties, such as phenyl, benzyl, naphthyl, anthracenyl, and the like,or may be substituted with one or more of hydroxyl, C₁₋₁₀-alkyl,C₂₋₁₀-alkenyl, C₂₋₁₀-alkynyl, and C₅₋₃₀-aryl, preferably isunsubstituted or hydroxyl-substituted, and more preferably isunsubstituted. Preferably, the condensed polymer has an organic polymerchain comprising as polymerized units, one or more second unsaturatedmonomers of formula (3) having a chromophore moiety. Preferredchromophore moieties are chosen from pyridyl, phenyl, naphthyl,acenaphthyl, fluorenyl, carbazolyl, anthracenyl, phenanthryl, pyrenyl,coronenyl, tetracenyl, pentacenyl, tetraphenyl, benzotetracenyl,triphenylenyl, perylenyl, benzyl, phenethyl, tolyl, xylyl, styrenyl,vinylnaphthyl, vinylanthracenyl, dibenzothiophenyl, thioxanthonyl,indolyl, acridinyl, biphenyl, phenoxy-phenyl, binaphthyl, and the like,and more preferably phenyl, naphthyl, anthracenyl, phenanthryl, benzyl,and the like. Chromophores used in the present invention are preferablyfree of aromatic rings having a substituent of the structure*—C(Rx)₂-O-Lg, wherein each Rx is independently H or a alkyl group of 1to 15 carbons, where each Rx may be taken together form an aliphaticring; Lg is H, an aliphatic monovalent hydrocarbon having 1 to 10carbons, or a monovalent aromatic group, and * indicates the point ofattachment to the aromatic ring.

Exemplary second unsaturated monomers include, without limitation: vinylaromatic monomers such as styrene, α-methylstyrene, β-methylstyrene,stilbene, vinylnaphthylene, acenaphthalene, and vinylpyridine;hydroxy-substituted vinyl aromatic monomers such as hydroxystyrene,o-courmaric acid, m-courmaric acid, p-courmaric acid, andhydroxyvinylnaphthylene; carboxyl-substituted vinyl aromatic monomerssuch as vinyl benzoic acid; ethylenically unsaturated carboxylic acidssuch as cinnamic acid, maleic acid, fumaric acid, crotonic acid,citraconic acid, itaconic acid, 3-pyridine (meth)acrylic acid, 2-phenyl(meth)acrylic acid, (meth)acrylic acid, 2-methylenemalonic acid,cyclopentenecarboxylic acid, methylcyclopentenecarboxylic acid,cyclohexenecarboxylic acid, and 3-hexene-1,6-dicarboxylic acid;hydroxyaryl esters of ethylenically unsaturated carboxylic acids, suchas hydroxyphenyl (meth)acrylate, hydroxybenzyl (meth)acrylate,hydroxynaphthyl (meth)acrylate, and hydroxyanthracenyl (meth)acrylate;ethylenically unsaturated anhydride monomers such as maleic anhydride,citraconic anhydride and itaconic anhudride, ethylenically unsaturatedimide monomers such as maleimide; ethylenically unsaturated carboxylicacid esters such as crotonic acid esters, itaconic acid esters, and(meth)acrylate esters; (meth)acrylonitrile; (meth)acrylamides; and thelike. Suitable (meth)acrylate ester monomers include, but are notlimited to, C₇₋₁₀-aralkyl (meth)acrylates, C₁₋₁₀-hydroxyalkyl(meth)acrylates, glycidyl (meth)acrylate, C₁₋₁₀-mercaptoalkyl(meth)acrylates, and C₁₋₁₀-alkyl (meth)acrylates. Exemplary(meth)acrylate ester monomers include, without limitation, benzylacrylate, benzyl methacrylate, hydroxyethyl acrylate, hydroxyethylmethacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,mercaptopropyl methacrylate, glycidyl methacrylate, methyl acrylate, andmethyl methacrylate.

It is preferred that the present condensed polymers have an organicpolymer chain comprising as polymerized units one or more firstunsaturated monomers of formula (2) and one or more second unsaturatedmonomers of formula (3), preferably one or more first unsaturatedmonomers of formula (2) and two or more second unsaturated monomers offormula (3), even more preferably one or more first unsaturated monomersof formula (2) and one or more second unsaturated monomers of formula(6), and still more preferably one or more first unsaturated monomers offormula (2), one or more second unsaturated monomers of formula (6), andone or more second unsaturated monomers of formula (3) having achromophore moiety. When the organic polymer chain of the presentcondensed polymers comprise as polymerized units one or more firstunsaturated monomers of formula (2) and one or more second unsaturatedmonomers of formula (3), such monomers are present in a mole ratio of1:99 to 99:1 of total monomers of formula (2) to total monomers offormula (3). Preferably, the mole ratio of the total monomers of formula(2) to the total monomers of formula (3) is from 95:5 to 5:95, morepreferably from 90:10 to 10:90, and yet more preferably from 50:50 to5:95. The one or more optional second unsaturated monomers may be usedin an amount from 0 to three times the molar amount of the total firstunsaturated monomers of formulae (1) and (2). When the present condensedpolymers comprise as polymerized units a relatively higher percentage ofsecond unsaturated monomers containing a chromophore, such polymers showreduced ability to be removed by wet stripping. It is preferred that thepresent condensed polymers comprise as polymerized units from 0 to 50mol % of second unsaturated monomers containing a chromophore.

Any condensable silicon monomer may be used to form the presentcondensed polymers, provided that the condensable silicon monomer isdifferent from the first unsaturated monomer having a condensablesilicon moiety, and that the condensable silicon monomer condenses withthe condensable silicon moiety pendently-bound to the organic polymerbackbone. As used herein, the term “backbone” refers to the main polymerchain. As used herein, “condensable silicon monomer” refers to a siliconmonomer having one or more condensable or hydrolyzable moieties. As usedherein, “condensable moiety” or “hydrolyzable moiety” refers to anymoiety capable to being condensed or hydrolyzed under conditions used toform the present condensed polymers. Exemplary condensable orhydrolyzable moieties include, but are not limited to, halogens, alkoxy,carboxylate, hydroxy, enoxy, oximino, amino, and the like. Suitablecondensable silicon monomers are those of formula (8)Si(R⁵⁰)_(p)(X)_(4-p)  (8)wherein p is an integer from 0 to 3; each R⁵⁰ is independently chosenfrom a C₁₋₃₀ hydrocarbyl moiety and a substituted C₁₋₃₀ hydrocarbylmoiety; and each X is independently chosen from halogen, C₁₋₁₀ alkoxy,—OH, —O—C(O)—R⁵⁰, and (O—Si(R⁵¹)₂)_(p2)—X¹; X¹ is independently chosenfrom halogen, C₁₋₁₀ alkoxy, —OH, —O—C(O)—R⁵⁰; each R⁵¹ is independentlychosen from R⁵⁰ and X; and p2 is an integer from 1 to 10. Preferably, pis an integer from 0 to 2, more preferably 0 to 1, and yet morepreferably p=0. X is preferably chosen from C₁₋₁₀-alkoxy, —OH,—O—C(O)—R⁵⁰, and (O—Si(R⁵¹)₂)_(p2)—X¹, and more preferably fromC₁₋₁₀-alkoxy and —OH. X¹ is preferably chosen from C₁₋₁₀-alkoxy and OH.The substituted C₁₋₃₀-hydrocarbyl moiety of R⁵⁰ refers to any C₁₋₃₀hydrocarbyl moiety having one or more of its hydrogens replaced with oneor more substituted moieties chosen from hydroxy, mercapto, C₁₋₂₀alkoxy, amino, C₁₋₂₀-alkylamino, di-C₁₋₂₀-alkylamino, cyano, halogen,epoxide, —C(═O)O—N(R¹⁷)₂, and C(═O)—O—C(═O)—R¹⁷, wherein each R′⁷ ischosen from H and C₁₋₂₀-alkyl. Suitable C₁₋₃₀-hydrocarbyl moieties ofR⁵⁰, without limitation, C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,C₃₋₃₀-cycloalkyl, and C₆₋₃₀-aryl, and preferably are C₁₋₂₀-alkyl,C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₃₋₂₀-cycloalkyl, and C₆₋₂₅-aryl. Siliconmonomers are often referred to by the number of hydrolyzable moietiesbonded to silicon in the monomer. For example, “M monomer” refers to asilicon monomer having one hydrolyzable moiety, such as monomers offormula (R⁵⁰)₃SiX, “D monomer” refers to a silicon monomer having twohydrolyzable moieties such as monomers of the formula (R⁵⁰)₂SiX₂, “Tmonomer” refers to a silicon monomer having three hydrolyzable moietiessuch as monomers of the formula R⁵⁰SiX₃, and “Q monomer” refers to a toa silicon monomer having four hydrolyzable moieties such as monomers ofthe formula SiX₄, wherein X and R⁵⁰ in each monomer are as describedabove. Any of M, D, T and Q monomers may be used individually or amixture of any of the foregoing may be used to prepare the presentcondensed polymers. Preferably, the condensable silicon monomer is oneor more monomers chosen from formulas (8a), (8b), (8c), and (8d)R⁵⁰ ₃SiX  (8a)R⁵⁰ ₂SiX₂  (8b)R⁵⁰SiX₃  (8c)SiX₄  (8d)wherein each X and R⁵⁰ are as described above for formula (8). It ispreferred that one or more Q monomers, that is, monomers of formula(8d), are used to prepare the present condensed polymers. Suchcondensable silicon monomers are generally commercially available andmay be used as is or may be further purified.

Condensable silicon monomers useful in forming the present condensedpolymers include, without limitation, methyltrichlorosilane,methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane,ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane,ethyltriacetoxysilane, propyltrichlorosilane, propyltrimethoxysilane,propyltriethoxysilane, propyltriacetoxysilane,hydroxypropyltrichlorosilane, hydroxypropyltrimethoxysilane,hydroxypropyltriethoxysilane, hydroxypropyltriacetoxysilane,mercaptopropyltrichlorosilane, mercaptopropyltrimethoxysilane,mercaptopropyltriethoxysilane, mercaptopropyltriacetoxy-silane,cyclopentyltrichlorosilane, cyclopentyltrimethoxysilane,cyclopentyltriethoxysilane, cyclopentyltriacetoxysilane,vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,vinyltriacetoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane,phenyltriethoxysilane, phenyltriacetoxysilane, biphenyltrichlorosilane,biphenyltrimethoxysilane, biphenyltriethoxysilane,biphenyltriacetoxysilane, dimethyldichlorosilane,dimethyldimethoxysilane, dimethyldiethoxysilane,dimethyldiacetoxysilane, diethyldichlorosilane, diethyldimethoxysilane,diethyldiethoxysilane, diethyldiacetoxysilane, diphenyldichlorosilane,diphenyldimethyoxy-silane, diphenyldiethoxysilane,diphenyldiacetoxysilane, methylphenyldichlorosilane,methylphenyldimethoxysilane, methylphenyldiethoxysilane,methylphenyldiacetoxysilane, methylvinyldichlorosilane,methylvinyldimethoxysilane, methylvinyldiethoxysilane,methylvinyldiacetoxysilane, divinyldichlososilane,divinyldimethoxysilane, divinyldiethoxysilane, divinyldiacetoxysilane,tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, andtetraacetoxysilane. Preferred curable silicon monomers aretetramethoxysilane and tetraethoxysilane.

Optionally, one or more etch selectivity improving agents may also becondensed with the one or more condensable silane monomers and the oneor more polymers described above. Suitable etch selectivity improvingagents are those of formula (9)G(X²)_(m4)  (9)wherein, G is an element from Groups 13 to 15 of the periodic tableexcluding carbon and silicon; each X² is independently halogen or OR⁵²;each R⁵² is independently H or an organic group having 1 to 30 carbonatoms; and m4 is equal to the valence of G. Preferably, R⁵² is chosenfrom H, C₁₋₁₀-alkyl, —C(O)—C₁₋₁₀-alkyl, and C₆₋₁₀-aryl, and morepreferably from H, C₁₋₁₀-alkyl, and —C(O)—C₁₋₁₀-alkyl. G is preferablyan element chosen from boron, aluminum, gallium, yttrium, germanium,titanium, zirconium, hafnium, bismuth, tin, phosphorous, vanadium,arsenic, antimony, niobium, and tantalum, more preferably from boron,aluminum, and germanium, and even more preferably G is boron. Suitablecompounds of formula (9) include, but are not limited to: trimethylborate, triethyl borate, tripropyl borate, tributyl borate, tripentylborate, trihexyl borate, tricyclopentyl borate, tricyclohexyl borate,triallyl borate, triphenyl borate, boron methoxyethoxide, boric acid,boron oxide; aluminum methoxide, aluminum ethoxide, aluminum propoxide,aluminum butoxide, aluminum amyloxide, aluminum hexyloxide, aluminumcyclopentoxide, aluminum cyclohexyloxide, aluminum allyloxide, aluminumphenoxide, aluminum ethoxyethoxide, aluminumdipropoxyethyl-acetoacetate, aluminum dibutoxyethyl-acetoacetate,aluminum propoxy-bis-ethyl-acetoacetate, aluminumbutoxy-bis-ethyl-acetoacetate, aluminum 2,4-pentanedionate, aluminum2,2,6,6-tetramethyl-3,5-heptanedionate, germanium methoxide, germaniumethoxide, germanium propoxide, germanium butoxide, germanium amyloxide,germanium hexyloxide, germanium cyclopentoxide, germaniumcyclohexyloxide, germanium allyloxide, germanium phenoxide, andgermanium ethoxyethoxide. Suitable etch selectivity improving agents arethose disclosed in U.S. Pat. No. 8,951,917.

Condensed polymers of the invention may be prepared by firstpolymerizing the one or more first unsaturated monomers and any optionalsecond unsaturated monomers according to methods well-known in the artto form an uncondensed polymer. Preferably, the present monomers arepolymerized by free-radical polymerization, such as those proceduresused for preparing (meth)acrylate or styrenic polymers. Any of a widevariety of free-radical initiators and conditions my be used. Othersuitable polymerization methods of preparing the polymers include,without limitation, Diels-Alder, living anionic, condensation,cross-coupling, RAFT, ATRP, and the like. Next, one or more uncondensedpolymers are subjected to conditions to condense and/or hydrolyze thecondensable silicon-containing moiety to form the present condensedpolymers. Such condensation and/or hydrolysis conditions are well-knownin the art and typically involve contacting the one or more uncondensedpolymers with aqueous acid or aqueous base, and preferably aqueous acid.For example, one or more of the present uncondensed polymers may becontacted with a composition comprising water, an acid, and optionallyone or more organic solvents, with optional heating. Preferred acids aremineral acids, such as HCl. The condensed polymers of the invention maybe partially condensed or fully condensed. By “partially condensed” itis meant that a portion of the condensable silicon-containing moietiespresent in the polymer have undergone a condensation or hydrolysisreaction. By “fully condensed” is meant that all condensablesilicon-containing moieties present in the polymer have undergone acondensation or hydrolysis reaction. The present uncondensed polymerstypically have a M_(w) of 1000 to 10000 Da, preferably from 2000 to 8000Da, and more preferably from 2500 to 6000 Da. The present condensedpolymers typically have any of 5000 to 75000 Da, preferably from 10000to 50000 Da, and more preferably from 20000 to 40000 Da. It will beappreciated by those skilled in the art that mixtures of condensedpolymers may suitably be used in the present process.

In addition to one or more of the above-described condensed polymers,the present compositions further comprise one or more crosslinkers freeof Si—O linkages and one or more organic solvents. Any crosslinker maybe suitably used in the present coating compositions, provided suchcrosslinker is free of Si—O linkages and has a plurality of functionalgroups capable of reacting with the condensed polymer upon curing. Thecrosslinker has at least 2 functional groups, preferably at least 3, andmore preferably at least 4, functional groups capable of reacting withthe condensed polymer upon curing. Exemplary functional groups capableof reacting with the condensed polymer upon curing include, withoutlimitation, hydroxyl groups, epoxy groups, oxetane groups, thiol groups,lactone moieties, isothiocyanate groups, anhydride moieties, maleimidemoieties, carboxylic acid groups, alkynyl groups, halogens, aldehydegroups, allyl ether moieties, imine groups, unsaturated ketone moieties,and the like. Preferred functional groups are hydroxyl groups.Preferably, the crosslinker has at least 2 of the same functional group,more preferably at least 3, and even more preferably at least 4 of thesame functional group. When the functional group is a hydroxyl group,such hydroxyl group may be a primary, secondary or tertiary aliphatichydroxyl group or an aromatic hydroxyl group, and more preferably aprimary aliphatic hydroxyl or a secondary aliphatic hydroxyl group.Suitable crosslinkers may be polymeric or non-polymeric. Polymericcrosslinkers useful in the present compositions may be linear, branched,star or dendritic polymers. When the crosslinker is polymeric, thefunctional groups capable of reacting with the condensed polymer uponcuring may be terminal groups on the polymer chain or be pendently-boundto the polymer chain, or a combination thereof. Preferably, thecrosslinker is a non-polymeric aliphatic polyol, a polymer havingpendently bound hydroxyl groups, or a mixture thereof. As an upperlimit, each terminus and/or each repeating unit of the polymericcrosslinker may have a functional group capable of reacting with thecondensed polymer upon curing. Preferably, up to 50 mol %, morepreferably up to 40 mol %, even more preferably up to 30 mol %, and yetmore preferably from 10 to 30 mol %, of the repeating units of thepolymeric crosslinker have a functional group capable of reacting withthe condensed polymer upon curing. Preferred polymeric crosslinkersuseful in the present invention are hydroxy-terminated alkylene oxidepolymers and polymers having pendently bound hydroxyl groups. Ingeneral, weight ratio of the condensed polymer to the crosslinker isfrom 95:5 to 60:40, preferably from 90:10 to 70:30, more preferably from85:15 to 70:30.

Suitable non-polymeric crosslinkers have at least 2 functional groups,preferably at least 3, more preferably at least 4, and still morepreferably 4 to 6, functional groups capable of reacting with thecondensed polymer upon curing. In general, non-polymeric crosslinkershave 10 or fewer functional groups capable of reacting with thecondensed polymer during curing. Typical non-polymeric crosslinkers arethose having an organic residue of 2 to 40, preferably 3 to 30, and morepreferably 4 to 30, carbon atoms and from 2 to 10 hydroxyl groups,preferably 2 to 8 hydroxyl groups, more preferably 3 to 8 hydroxylgroups, and yet more preferably 4 to 6 hydroxyl groups. Optionally, thesuitable non-polymeric crosslinkers may be alkoxylated, that is they maybe reacted with, on average, less than or equal to 2 moles of alkyleneoxide, such as ethylene oxide and/or propylene oxide, per hydroxylgroup. By way of example, if the non-polymeric crosslinker has 4hydroxyl groups, such as pentaerythritol, it may be reacted with up to 8moles of alkylene oxide (that is, an average 2 moles of alkylene oxideper hydroxyl group). Exemplary non-polymeric crosslinkers are, withoutlimitation, glycerol, trimethylol ethane, trimethylol propane,erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol,di(trimethylolpropane), 2-hydroxymethyl-1,3-propanediol, sorbitol,xylitol, ethoxylated glycerol having 2 to 6 moles of ethylene oxide,propoxylated glycerol having 2 to 6 moles of propylene oxide,ethoxylated trimethylol ethane having 2 to 6 moles of ethylene oxide,propoxylated trimethylol ethane having 2 to 6 moles of propylene oxide,ethoxylated trimethylol propane having 2 to 6 moles of ethylene eoxide,propoxylated trimethylol propane having 2 to 6 moles of propylene oxide,ethoxylated erythritol having 3 to 8 moles of ethylene oxide,propoxylated erythritol having 3 to 8 moles of propylene oxide,ethoxylated pentaerythritol having 3 to 8 moles of ethylene oxide,propoxylated pentaerythritol having 3 to 8 moles of propylene oxide,ethoxylated dipentaerythritol having 4 to 12 moles of ethylene oxide,propoxylated dipentaerythritol having 4 to 12 moles of propylene oxide,ethoxylated tripentaerythritol having 6 to 16 moles of ethylene oxide,propoxylated tripentaerythritol having 6 to 16 moles of propylene oxide,ethoxylated di(trimethylolpropane) having 3 to 8 moles of ethyleneoxide, propoxylated di(trimethylolpropane) having 3 to 8 moles ofpropylene oxide, and mixtures thereof. Preferred non-polymericcrosslinkers are trimethylol propane, erythritol, pentaerythritol,dipentaerythritol, tripentaerythritol, 2-hydroxymethyl-1,3-propanediol,ethoxylated trimethylol ethane having 2 to 6 moles of ethylene oxide,propoxylated trimethylol ethane having 2 to 6 moles of propylene oxide,ethoxylated trimethylol propane having 2 to 6 moles of ethylene eoxide,propoxylated trimethylol propane having 2 to 6 moles of propylene oxide,ethoxylated erythritol having 3 to 8 moles of ethylene oxide,propoxylated erythritol having 3 to 8 moles of propylene oxide,ethoxylated pentaerythritol having 3 to 8 moles of ethylene oxide,propoxylated pentaerythritol having 3 to 8 moles of propylene oxide,ethoxylated dipentaerythritol having 4 to 12 moles of ethylene oxide,propoxylated dipentaerythritol having 4 to 12 moles of propylene oxide,ethoxylated tripentaerythritol having 6 to 16 moles of ethylene oxide,propoxylated tripentaerythritol having 6 to 16 moles of propylene oxide,ethoxylated di(trimethylolpropane) having 3 to 8 moles of ethyleneoxide, propoxylated di(trimethylolpropane) having 3 to 8 moles ofpropylene oxide, and mixtures thereof

One class of polymeric crosslinkers useful in the present compositionsare alkylene oxide polymers having C₂₋₄-alkyleneoxy repeating units and2 or more terminal hydroxyl groups, and polymers having pendently boundhydroxyl groups. Preferred alkylene oxide polymers have 3 or moreterminal hydroxyl groups, and more preferably 4 or more terminal hydroxygroups. Exemplary alkyleneoxy repeating units are ethyleneoxy,propyleneoxy, butyleneoxy, and combinations thereof. Preferred alkyleneoxide polymers are glycerol ethoxylate having an average of 3-30ethyleneoxy units, glycerol propxylate having an average of 3-30propyleneoxy units, trimethylolpropane ethoxylate having an average of3-30 ethyleneoxy units, trimethylolpropane propxylate having an averageof 3-30 propyleneoxy units, pentaerythritol ethoxylate having an averageof 3-30 ethyleneoxy units, pentaerythritol propxylate having an averageof 3-30 propyleneoxy units, pentaerythritol ethoxylate/propoxylatehaving an average of 3-30 ethyleneoxy units and an average of 3-30propyleneoxy units, dipentaerythritol ethoxylate having an average of4-30 ethyleneoxy units, dipentaerythritol propxylate having an averageof 4-30 propyleneoxy units, and combinations thereof.

Preferred polymeric crosslinkers useful in the present compositions arepolymers having pendently bound hydroxyl groups, and preferably compriseas polymerized units one or more unsaturated monomers having ahydroxy-substituted moiety of the formula *-L³-0H, where * denotes thepoint of attachment to the monomer; and L³ is a C₁₋₃₀-divalent linkinggroup. Preferably, the polymeric crosslinkers havinghydroxyl-substituted pendent groups comprise as polymerized units one ormore monomers of formula (10)

wherein R⁶⁰ and R⁶¹ are independently H, C₁₋₁₀-alkyl, C₆₋₂₀-aryl,C₁₋₁₀-haloalkyl, halogen, or -L³-OH; R⁶² is H, C₁₋₄-alkyl,C₁₋₄-haloalkyl, halogen, CN, or -L³-OH; and L³ is a C₁₋₃₀-divalentlinking group. It is preferred that R⁶⁰ and R⁶¹ are independently H or-L³-OH, and more preferably H. Preferably, R⁶² is H, C₁₋₄-alkyl,C₁₋₄-haloalkyl, halogen, or CN; and more preferably H or methyl. L³ ispreferably a C₁₋₃₀-organic residue optionally having from 1 to 10heteroatoms. Preferred monomers of formula (10) are C₂₋₁₀-hydroxyalkyl(meth)acrylates of formula (10A) and alkyleneoxy (meth)acrylates offormula (10B)

wherein R^(62a) is H or methyl; R⁶³ is C₂₋₁₀-alkylene; R^(62b) is H ormethyl; and p4 is the average number of O—C₂₋₃-alkylene units and is aninteger from 1 to 10. Exemplary monomers of formulae (10A) and (10B) arehydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropylacrylate, hydroxypropyl methyacrylate, ethoxylated (meth)acrylate havingan average of 1-10 ethyleneoxy units, and propoxylated (meth)acrylatehaving an average of 1-10 propyleneoxy units. Preferred polymericcrosslinkers having pendently bound hydroxy groups are those comprisingas polymerized units one or more monomers of formula (10) and one ormore monomers chosen from (meth)acrylic acid, C₁₋₂₀-alkyl(meth)acrylates, C₆₋₂₀-aryl (meth)acrylates, C₇₋₂₀-arylalkyl(meth)acrylates, vinyl aromatic monomers, monomers of formula (4), andmonomers of formula (6)

wherein ADG is an acid decomposable group as described above; each ofR²⁰ and R^(20a) is independently chosen from H, C₁₋₄-alkyl,C₁₋₄-haloalkyl, halogen, and CN; and R³⁰ is a monovalent organic residuehaving a lactone moiety as described above. Preferably, the polymericcrosslinkers comprise as polymerized units from 5 to 50 mol %, morepreferably 5 to 40 mol %, even more preferably 5 to 30 mol %, and yetmore preferably from 10 to 30 mol %, of monomers of formula (10). Otherpreferred monomers of formula (10) include hydroxystyrene andhydroxy(vinylnaphthalene).

A variety of organic solvents and water may be used in the presentcompositions, provided that such solvent dissolves the components of thecomposition. Preferably, the present compositions comprise one or moreorganic solvents and optionally water. Organic solvents may be usedalone or a mixture of organic solvents may be used. Suitable organicsolvents include, but are not limited to; ketones such as cyclohexanoneand methyl-2-n-amylketone; alcohols such as 3-methoxybutanol,3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and1-ethoxy-2-propanol; ethers such as propylene glycol methyl ether(PGME), propylene glycol ethyl ether (PGEE), ethylene glycol monomethylether, propylene glycol monoethyl ether, ethylene glycol monoethylether, propylene glycol dimethyl ether, and diethylene glycol dimethylether; esters such as propylene glycol monomethyl ether acetate (PGMEA),propylene glycol monoethyl ether acetate, ethyl lactate (EL), methylhydroxyisobutyrate (HBM), ethyl pyruvate, butyl acetate, methyl3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate,tert-butyl propionate, and propylene glycol mono-tert-butyl etheracetate; lactones such as gamma-butyrolactone; ionic liquids; and anycombination of the foregoing. Preferred solvents are PGME, PGEE, PGMEA,EL, HBM, and combinations thereof.

The present compositions may further comprise one or more optionalcomponents, such as cure catalysts, coating enhancers, one or morestabilizers, and the like. The amount of such optional components usedin the present compositions is well within the ability of those skilledin the art.

Suitable cure catalysts include, but are not limited to, thermal acidgenerators, photoacid generators, photobase generators, and quaternaryammonium salts, preferably thermal acid generators and quaternaryammonium salts, and more preferably quaternary ammonium salts. A thermalacid generator is any compound which liberates acid upon exposure toheat. Thermal acid generators are well-known in the art and aregenerally commercially available, such as from King Industries, Norwalk,Conn. Exemplary thermal acid generators include, without limitation,amine blocked strong acids, such as amine blocked sulfonic acids likeamine blocked dodecylbenzenesulfonic acid. A wide variety of photoacidgenerators are known in the art and are also generally commerciallyavailable, such as from Wako Pure Chemical Industries, Ltd., and fromBASF SE. Suitable quaternary ammonium salts are: quaternary ammoniumhalides; quaternary ammonium carboxylates; quaternary ammoniumsulfonates; quaternary ammonium bisulfates; and the like. Preferredquaternary ammonium salts include; benzyltrialkylammonium halides suchas benzyltrimethylammonium chloride and benzyltriethylammonium chloride;tetraalkylammonium halides such as tetramethylammonium halides,tetraethylammonium halides, and tetrabutylammonium halides;tetraalkylammonium carboxylates such as tetramethylammonium formate,tetramethylammonium acetate, tetramethylammonium triflate,tetrabutylammonium acetate, and tetrabutylammonium triflate;tetraalkylammonium sulfonates such as tetramethylammonium sulfonate andtetrabutylammonium sulfonate; and the like. Preferred cure catalysts aretetraalkylammonium halides, and more preferably tetraalkylammoniumchlorides. Such quaternary ammonium salts are generally commerciallyavailable, such as from Sigma-Aldrich, or may be prepared by proceduresknown in the art. Such optional curing catalysts are used in the presentcompositions in an amount of from 0 to 10% of total solids, preferablyfrom 0.01 to 7% of total solids, and more preferably from 0.05 to 5% oftotal solids.

Coating enhancers are optionally added to the present compositions toimprove the quality of a film or layer of the composition that is coatedon a substrate. Such coating enhancers may function as plasticizers,surface leveling agents, and the like. Such coating enhancers arewell-known to those skilled in the art, and are generally commerciallyavailable. Exemplary coating enhancers are: long chain alkanols such asoleyl alcohol, cetyl alcohol, and the like; glycols such as tripropyleneglycol, tetraethylene glycol, and the like; and surfactants. While anysuitable surfactant may be used as a coating enhancer, such surfactantsare typically non-ionic. Exemplary non-ionic surfactants are thosecontaining an alkyleneoxy linkage, such as ethyleneoxy, propyleneoxy, ora combination of ethyleneoxy and propyleneoxy linkages. It is preferredthat one or more coating enhancers are used in the present compositions.The coating enhancers are typically used in the present compositions inan amount of 0 to 10% of total solids, preferably from 0.5 to 10% oftotal solids, and more preferably from 1 to 8% of total solids.

One or more stabilizers may optionally be added to the presentcompositions. Such stabilizers are useful for preventing unwantedhydrolysis or condensation of the silicon-containing moieties duringstorage. A variety of such stabilizers are known, and preferably thesilicon-containing polymer stabilizer is an acid. Suitable acidstabilizers for the siloxane polymers include, without limitation,carboxylic acids, carboxylic acid anhydrides, mineral acids, and thelike, and mixtures of any of the forgoing. Exemplary stabilizers includeacetic acid, oxalic acid, malonic acid, malonic anhydride, malic acid,maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaricacid, glutaric anhydride, adipic acid, succinic acid, succinicanhydride, nitric acid and mixtures thereof. Carboxylic acids arepreferred stabilizers, and more preferably the stabilizers are aceticacid, oxalic acid, malonic acid, malic acid, maleic acid, fumaric acid,citraconic acid, glutaric acid, adipic acid, succinic acid, and mixturesthereof. Such stabilizers are used in an amount of 0 to 20% of totalsolids, preferably from 0.1 to 15% of total solids, more preferably from0.5 to 10% of total solids, and yet more preferably from 1 to 10% oftotal solids.

The compositions of the invention are prepared by combining the one ormore present condensed polymers; one or more solvents; and any optionalcomponents, in any order. The compositions may be used as is, or may befurther purified, such as by filtration.

The process of the present invention comprises (a) coating a substratewith the composition described above to form a coating layer; (b) curingthe coating layer to form a polymeric underlayer; (c) disposing a layerof a photoresist on the polymeric underlayer; (d) pattern-wise exposingthe photoresist layer to form a latent image; (e) developing the latentimage to form a patterned photoresist layer having a relief imagetherein; (f) transferring the relief image to the substrate; and (g)removing the polymeric underlayer by wet stripping.

A coating layer comprising the present compositions may be coated on anelectronic device substrate by any suitable means, such as spin-coating,slot-die coating, doctor blading, curtain coating, roller coating, spraycoating, dip coating, and the like. Spin-coating is preferred. In atypical spin-coating method, the present compositions are applied to asubstrate which is spinning at a rate of 500 to 4000 rpm for a period of15 to 90 seconds to obtain a desired layer of the condensed polymer onthe substrate. It will be appreciated by those skilled in the art thatthe thickness of the condensed polymer mixture layer may be adjusted bychanging the spin speed, as well as the solids content of thecomposition.

A wide variety of electronic device substrates may be used in thepresent invention, such as: packaging substrates such as multichipmodules; flat panel display substrates; integrated circuit substrates;substrates for light emitting diodes (LEDs) including organic lightemitting diodes (OLEDs); semiconductor wafers; polycrystalline siliconsubstrates; and the like. Such substrates are typically composed of oneor more of silicon, polysilicon, silicon oxide, silicon nitride, siliconoxynitride, silicon germanium, gallium arsenide, aluminum, sapphire,tungsten, titanium, titanium-tungsten, nickel, copper, and gold.Suitable substrates may be in the form of wafers such as those used inthe manufacture of integrated circuits, optical sensors, flat paneldisplays, integrated optical circuits, and LEDs. As used herein, theterm “semiconductor wafer” is intended to encompass “an electronicdevice substrate,” “a semiconductor substrate,” “a semiconductordevice,” and various packages for various levels of interconnection,including a single-chip wafer, multiple-chip wafer, packages for variouslevels, or other assemblies requiring solder connections. Suchsubstrates may be any suitable size. Preferred wafer substrate diametersare 200 mm to 300 mm, although wafers having smaller and largerdiameters may be suitably employed according to the present invention.As used herein, the term “semiconductor substrate” includes anysubstrate having one or more semiconductor layers or structures whichmay optionally include active or operable portions of semiconductordevices. A semiconductor device refers to a semiconductor substrate uponwhich at least one microelectronic device has been or is being batchfabricated.

After being coated on the substrate, the coating layer is optionallysoft-baked at a relatively low temperature to remove any solvent andother relatively volatile components from the underlayer. Typically, thesubstrate is baked at a temperature of ≤200° C., preferably from 100 to200° C., and more preferably from 100 to 150° C. The baking time istypically from 10 seconds to 10 minutes, preferably from 30 seconds to 5minutes, and more preferably from 60 to 90 seconds. When the substrateis a wafer, such baking step may be performed by heating the wafer on ahot plate. Such soft-baking step may be performed as part of the curingof the coating layer, or may be omitted altogether.

The coating layer comprising the present condensed polymers andcrosslinkers is then cured to form an underlayer. The coating layer issufficiently cured such that the film does not intermix with asubsequently applied organic layer, such as a photoresist or otherorganic layer disposed directly on the coating layer, while stillmaintaining the desired antireflective properties (n and k values) andetch selectivity of the underlayer film. The coating layer may be curedin an oxygen-containing atmosphere, such as air, or in an inertatmosphere, such as nitrogen and under conditions, such as heating,sufficient to provide a cured underlayer. This curing step is conductedpreferably on a hot plate-style apparatus, although oven curing may beused to obtain equivalent results. Typically, such curing is performedby heating the condensed polymer layer at a curing temperature of ≤350°C., and preferably 200 to 250° C. Alternatively, a two-step curingprocess or a ramped temperature curing process may be used. Suchtwo-step and ramped temperature curing conditions are well-known tothose skilled in the art. The curing temperature selected should besufficient for any thermal acid generator used to liberate acid to aidin curing of the condensed polymer film. The curing time may be from 10seconds to 10 minutes, preferably from 30 seconds to 5 minutes, morepreferably from 45 seconds to 5 minutes, and yet more preferably from 45to 90 seconds. The choice of final curing temperature depends mainlyupon the desired curing rate, with higher curing temperatures requiringshorter curing times. Following this curing step, the underlayer surfacemay optionally be passivated by treatment with a passivating agent suchas a disilazane compound, such as hexamethyldisilazane, or by adehydration bake step to remove any adsorbed water. Such passivatingtreatment with a disilazane compound is typically performed at 120° C.

After curing of the coating layer comprising the condensed polymer andcrosslinker to form an underlayer, one or more processing layers, suchas photoresists, hardmask layers, bottom antireflective coating (orBARC) layers, and the like, may be disposed on the underlayer. Forexample, a photoresist layer may be disposed, such as by spin coating,directly on the surface of the underlayer. Alternatively, a BARC layermay be coated directly on the underlayer, followed by curing of the BARClayer, and coating a photoresist layer directly on the cured BARC layer.In another alternative, an organic underlayer is first coated on asubstrate and cured, a condensed polymer layer of the invention is thencoated on the cured organic underlayer, the coating layer is then curedto form an underlayer, an optional BARC layer may be coated directly onthe underlayer, followed by curing of the optional BARC layer, andcoating a photoresist layer directly on the cured BARC layer. A widevariety of photoresists may be suitably used, such as those used in 193nm lithography, such as those sold under the EPIC™ brand available fromDow Electronic Materials (Marlborough, Mass.). Suitable photoresists maybe either positive tone development or negative tone developmentresists, or may be conventional negative resists. The photoresist layeris then imaged (exposed) using patterned actinic radiation, and theexposed photoresist layer is then developed using the appropriatedeveloper to provide a patterned photoresist layer. An advantage of thepresent invention is that pattern collapse of the patterned photoresistlayer upon contact with developer is reduced as compared to conventionalwet-strippable silicon-containing underlayers. The pattern is nexttransferred from the photoresist layer to any optional BARC layer, andthen to the underlayer by an appropriate etching technique, such as dryetching with an appropriate plasma. Typically, the photoresist is alsoremoved during such etching step. Next, the pattern is transferred toany organic underlayer present using an appropriate technique, such asdry etching with O₂ plasma, and then to the substrate as appropriate.Following these pattern transfer steps, the underlayer, and any optionalorganic underlayers are removed using conventional techniques. Theelectronic device substrate is then further processed according toconventional means.

The coating layers comprising the present condensed polymers andunderlayers described herein are wet strippable. By “wet strippable” ismeant that the coating layers and underlayers of the invention areremoved, and preferably substantially removed (≥95% of film thickness),by contacting the coating layer or underlayer with conventional wetstripping compositions, such as: (1) an aqueous base composition, suchas aqueous alkali (typically about 5%) or aqueous tetramethylammoniumhydroxide (typically ≥5 wt %), (2) aqueous fluoride ion strippers suchas ammonium fluoride/ammonium bifluoride mixtures, (3) a mixture ofmineral acid, such as sulfuric acid or hydrochloric acid, and hydrogenperoxide, or (4) a mixture of ammonia, water and optionally hydrogenperoxide. A particular advantage of the present polymers, andparticularly of the present underlayers, is that they are wet strippableupon contact with a mixture of ammonia and hydrogen peroxide. A suitablemixture of sulfuric acid and hydrogen peroxide is concentrated sulfuricacid+30% hydrogen peroxide. A wide range of ammonia and water mixturesmay be used. A suitable mixture of ammonia, water and hydrogen peroxideis a mixture of ammonia+hydrogen peroxide+water in a weight ratio of1:1:5 to 1:10:50, such as ratios of 1:1:10, 1:1:40, 1:5:40 or 1:1:50.Typically, such mixtures are used at temperatures of from roomtemperature to about 75° C. Preferably, ≥97%, and more preferably ≥99%,of the film thickness of the polymer layer or underlayer is removed bycontacting the polymer layer or siloxane underlayer with either (i)mixture of sulfuric acid and hydrogen peroxide or (ii) a mixture ofammonium hydroxide and hydrogen peroxide.

Another advantage of the present polymer layers is that they are easilyremoved to allow re-work of the substrate, such as a wafer. In such are-work process, a composition described above comprising one or morecondensed polymers of the invention is coated on a substrate. The coatedpolymer layer is then optionally soft-baked, and then cured to form anunderlayer. Next, a photoresist layer is coated on the underlayer, andthe resist layer is imaged and developed. The patterned resist layer andthe underlayer may then each be removed to allow the wafer to bere-worked. The underlayer is contacted with any of the above-describedwet stripping compositions, such as aqueous tetramethylammoniumhydroxide compositions (typically ≥5 wt %) and aqueous fluoride ionstrippers such as ammonium fluoride/ammonium bifluoride mixtures, at asuitable temperature to remove the underlayer to provide the substratefree, or substantially free, of underlayer and readily undergoadditional re-work as may be necessary. Such re-work includes coatinganother layer of the present condensed polymers on the substrate andprocessing the polymer coating as described above.

EXAMPLE 1

A solution of tert-butyl methacrylate (tBMA), (173 g), gammabutyrolactone (GBLMA), (166 g) and 3-(trimethoxysilyl)propylmethacrylate (TMSPMA), (60.6 g) dissolved in 1,3-dioxolane (304 g) and asolution of V-65 initiator (60.6 g) dissolved in 2:1 v/vtetrahydrofurane/acetonitrile (60.6 g) were both added dropwise over 2hr. to 3-dioxolane (710 g) at 75° C. under a nitrogen blanket. Afteraddition the reaction solution was held at 75° C. for an additional twohours, cooled to room temperature and precipitated into heptanes:MTBE(1:1 v/v, 14 L). The precipitated polymer was collected by vacuumfiltration and vacuum oven dried for 24 hours to afford Polymer 1(tBMA/GBLMA/TMSPMA 50/40/10) as a white solid (271 g, 68%). M, wasdetermined by GPC relative to polystyrene standard and was found to be5700 Da.

EXAMPLE 2

Polymers 2 to 12, reported in Table 2 below, were synthesized accordingto the procedure of Example 1 using the monomers listed in Table 1below. The amount of each monomer used is reported in Table 2 in mol %.Polymers 2 to 12 were isolated in 20-99% yield and had the M, reportedin Table 2.

TABLE 1

TABLE 2 Monomer Monomer Monomer Monomer Monomer Polymer A (mol %) B (mol%) C (mol %) D (mol %) E (mol %) M_(w)  2 Monomer 1 Monomer 2 Monomer 314000  (10) (50) (40)  3 Monomer 1 Monomer 2 Monomer 3 Monomer 4 5400(10) (50) (25) (15)  4 Monomer 1 Monomer 2 Monomer 4 Monomer 6 5100 (10)(55) (20) (15)  5 Monomer 1 Monomer 2 Monomer 3 Monomer 6 5400 (10) (50)(25) (15)  6 Monomer 1 Monomer 2 Monomer 3 Monomer 4 Monomer 6 4300 (10)(50) (25) (5) (10)  7 Monomer 1 Monomer 2 Monomer 3 4000 (10) (40) (50) 8 Monomer 1 Monomer 2 Monomer 3 Monomer 7 4000 (10) (40) (40) (10)  9Monomer 1 Monomer 2 Monomer 3 4300 (20) (50) (30) 10 Monomer 1 Monomer 2Monomer 3 Monomer 4 Monomer 8 4900 (10) (50) (25) (5) (10) 11 Monomer 1Monomer 2 Monomer 5 Monomer 6 5700 (10) (50) (25) (15) 12 Monomer 1Monomer 2 Monomer 5 Monomer 4 Monomer 6 6800 (10) (50) (25) (5) (10)

EXAMPLE 3

The procedure of Example 2 is repeated and is expected to providePolymers 13-18 reported in Table 3. The monomer numbers reported inTable 3 refer to the monomers in Table 1 of Example 2.

TABLE 3 Monomer A Monomer B Monomer C Monomer D Monomer E Polymer (mol%) (mol %) (mol %) (mol %) (mol %) 13 Monomer 1 Monomer 2 Monomer 3Monomer 4 (5) Monomer 9 (10) (50) (25) (10) 14 Monomer 2 Monomer 3Monomer 4 Monomer 12 (45) (25) (15) (15) 15 Monomer 2 Monomer 4 Monomer5 Monomer 8 Monomer 11 (30) (25) (25) (10) (10) 16 Monomer 4 Monomer 7Monomer 9 (5) Monomer 11 Monomer 14 (25) (25) (10) (35) 17 Monomer 2Monomer 3 Monomer 4 Monomer 13 (50) (25) (15) (10) 18 Monomer 1 (5)Monomer 2 Monomer 4 Monomer 5 Monomer 13 (50) (15) (20) (10)

EXAMPLE 4

A solution of hydrochloric acid (37 wt % in water, 7.76 g) in water(25.9 g) was added over 10 minutes to a mixture of TEOS (63.5 g, 50 mol%) and Polymer 1 from Example 1 (50.0 g, 50 mol %) in THF (270 g) andstirred at room temperature for 1 hr. The reaction mixture was heated to63° C. for 20 hr. and then cooled to room temperature. PGEE (200 g) wasadded, the volatile species removed under reduced pressure, and theresulting solution was diluted with PGEE to provide Condensed Polymer 1(10 wt % in PGEE, 600 g) as a clear solution. M_(w) was determined byGPC relative to polystyrene standards (28,100 Da).

EXAMPLE 5

Condensed Polymers 2 to 26, reported in Table 5 below, were synthesizedaccording to the procedure of Example 4 using Polymers 1 to 12 fromExamples 1 and 2 and the monomers listed in Table 4 below. The amount ofeach monomer used is reported in Table 5 in mol %. Condensed Polymers 2to 12 were isolated in 20-99% yield and had the M_(w) reported in Table5.

TABLE 4

TABLE 5 Condensed Polymer Monomer A Monomer B Monomer D Polymer (mol %)(mol %) (mol %) (mol %) M_(w) 2 1 (45) Monomer 1S 22,700 (55) 3 1 (26)Monomer 1S Monomer 2S Monomer 3S 12,400 (50)  (9) (15) 4 1 (50) Monomer1S 52,800 (50) 5 1 (50) Monomer 1S 40,300 (50) 6 3 (50) Monomer 1S26,600 (50) 7 2 (50) Monomer 1S 100,000 (50) 8 2 (50) Monomer 1S 30,000(50) 9 4 (50) Monomer 1S 20,000 (50) 10 5 (50) Monomer 1S 22,000 (50) 116 (50) Monomer 1S 20,500 (50) 12 6 (50) Monomer 1S Monomer 2S 11,100(40) (10) 13 9 (40) Monomer 1S Monomer 2S 25,000 (50) (10) 14 1 (40)Monomer 1S 27,700 (60) 15 1 (30) Monomer 1S 25,700 (70) 16 7 (50)Monomer 1S 29,000 (50) 17 8 (50) Monomer 1S 27,000 (50) 18 1 (60)Monomer 1S 40,600 (40) 19 9 (50) Monomer 1S 39,900 (50) 20 1 (30)Monomer 1S Monomer 2S 24,000 (65)  (5) 21 11 (50)  Monomer 1S 20,200(50) 22 12 (50)  Monomer 1S 18,700 (50) 23 1 (50) Monomer 1S Monomer 4S25,000 (40) (10) 24 1 (50) Monomer 1S Monomer 5S 25,000 (40) (10) 25 1(50) Monomer 1S Monomer 6S 44,000 (40) (10) 26 1 (50) Monomer 1S Monomer7S 24,600 (40) (10)

EXAMPLE 6

The following components were combined: 1.6 wt % of Condensed Polymer 1;0.09 wt % of a 0.1 wt % solution of tetrabutylammonium chloride in PGEE;49 wt % of PGEE; 49.2 wt % of 2-hydroxyisobutyric acid methyl ester;0.009 wt % acetic acid; and 0.2 wt % coating enhancer. The mixture wasfiltered through 0.2 μm polytetrafluoroethylene syringe to provideComparative Formulation 1.

EXAMPLE 7

The procedure of Example 6 was repeated to prepare ComparativeFormulations 2 to 8 by replacing Condensed Polymer 1 with the CondensedPolymers reported in Table 6.

TABLE 6 Comparative Formulation Condensed Polymer 2 Condensed Polymer 63 Condensed Polymer 7 4 Condensed Polymer 23 5 Condensed Polymer 24 6Condensed Polymer 25 7 Condensed Polymer 10 8 Condensed Polymer 11

EXAMPLE 8

The procedure of Example 6 was repeated except that Condensed Polymer 1was replaced with a 85/15 w/w mixture of Condensed Polymer 1 andpropoxylated pentaerythritol having on average 5 moles of propyleneoxide (formula (11), a+b+c+d≈5) as a crosslinker to provide Formulation1.

EXAMPLE 9

The procedure of Example 6 was repeated to provide Formulations 2 to 15by replacing Condensed Polymer 1 with the condensed polymer/crosslinkermixtures reported in Table 7. Crosslinker C1 is propoxylatedpentaerythritol having on average 5 moles of propylene oxide of formula(11). Crosslinker C2 is a polymer of tert-butylmethacrylate/alpha-gammabutyrolactone methacrylate/hydroxyethylmethacrylate/methacrylic acid in a mole ratio of 25/25/25/25.Crosslinker C3 is a polymer of tert-butylmethacrylate/alpha-gammabutyrolactone methacrylate/hydroxyethylmethacrylate in a mole ratio of 50/25/25. Crosslinker C4 is polymer ofmethacrylic acid and hydroxyethyl methacrylate in a mole ratio of 60/40.

TABLE 7 Condensed Condensed Polymer/Crosslinker Formulation PolymerCrosslinker (w/w) 2 1 C1 85/15 3 1 C2 85/15 4 1 C3 85/15 5 23 C1 85/15 624 C1 85/15 7 25 C1 85/15 8 6 C1 85/15 9 7 C1 85/15 10 10 C1 85/15 11 10C4 85/15 12 11 C4 95/5  13 11 C4 90/10 14 11 C4 85/15 15 11 C1 85/15

EXAMPLE 10

Comparative Formulations from Examples 6 and 7 and Formulations of theinvention from Examples 8 and 9 were spin-coated on a bare 200 mmsilicon wafers at 1500 rpm and baked at 240° C. for 60 seconds using anACT-8 Clean Track (Tokyo Electron Co.). The thickness of each coatedfilm after baking of was measured with an OptiProbe™ instrument fromTherma-wave Co. Each coated sample was then evaluated for SC-1 wetstrippability using a 1/1/40 wt/wt/wt mixture of 30% NH₄OH/30%H₂O₂/water. The SC-1 mixture was heated to 60° C., and coupons of eachcoated wafer were immersed into the solution for 1 min. The coupons wereremoved from the SC-1 mixture and rinsed with deionized water, and thefilm thickness was again measured. The film thickness loss for eachsample was calculated as the difference in film thickness before andafter contact with the stripping agent. A separate film prepared asdescribed above was optionally tested for SC-1 strippability afteretching. Etching was performed for 60 seconds using RIE790 fromPlasma-Therm Co. with oxygen gas, 25 sscm flow, 180 W of power, and 6mTorr of pressure. The stripping results, obtained as the rate of filmremoval in A/min, are reported in Table 8.

Comparative Formulations from Examples 6 and 7 and Formulations of theinvention from Examples 8 and 9, at either 1.7% or 3.5% solids, werecoated on 200 mm silicon wafers as described above with a targetthickness of 400 Å or 1000 Å and measured (post cure) as describedabove. A puddle of commercially available 0.26N TMAH developer (MFCD-26) was applied to each wafer for 60 seconds, after which the waferswere rinsed with DI water, spin dried and the film thickness wasre-measured. A final drying bake of 105° C./60 seconds was applied toeach wafer and final film thickness was measured. The thickness loss ofeach film, reported as the rate of film removal in A/min, resulting fromthis TMAH strip is reported in Table 8. A negative film strip valueindicates an increase in film thickness.

TABLE 8 Before Etch After Etch TMAH Strip Formulation Example (Å/min)(Å/min) (Å/min) Comparative Formulation 1 >394 >242 −41 1 905 546 −10 2754 415 −4 3 807 475 −4 4 759 422 −9 Comparative Formulation 2 409 466−19 8 210 423 −4 Comparative Formulation 3 190 452 −50 9 140 184 −7Comparative Formulation 4 110 114 −25 5 38 96 −3 Comparative Formulation5 87 99 −21 6 64 84 −2 Comparative Formulation 6 90 98 −6 7 74 89 −2Comparative Formulation 7 113 409 −13 10 41 145 0 11 116 381 −4Comparative Formulation 8 226 428 −16 12 158 433 −12 13 134 414 −2 14 86194 0 15 89 395 1

What is claimed is:
 1. A composition comprising: (a) one or moresolvents; (b) a condensate and/or hydrolyzate of (i) one or morecondensed silicon-containing polymers comprising as polymerized unitsone or more first unsaturated monomers having a condensablesilicon-containing moiety, wherein the condensable silicon-containingmoiety is pendent to a backbone of the polymer, the one or more firstunsaturated monomers having the formula (1)

wherein L is a single bond or a divalent linking group; each R¹ isindependently chosen from H, C₁₋₁₀-alkyl, C-alkenyl, C₅₋₂₀-aryl, andC₆₋₂₀-aralkyl; each of R² and R³ are independently chosen from H, C₁₋₄alkyl, C₁₋₄ haloalkyl, halogen, C₅₋₂₀-aryl, C₆₋₂₀ aralkyl, and CN; R⁴ ischosen from H, C₁₋₁₀ alkyl, C₁₋₁₀ haloalkyl, halogen, C₅₋₂₀-aryl, C₆₋₂₀aralkyl, and C(═O)R⁵; R⁵ is chosen from OR⁶ and N(R⁷)₂; R⁶ is chosenfrom H, and C₁₋₂₀ alkyl; each R⁷ is independently chosen from H, C₁₋₂₀alkyl, and C₆₋₂₀ aryl; each Y¹ is independently chosen from halogen,C₁₋₁₀-alkoxy, C₅₋₁₀-aryloxy, and C₁₋₁₀-carboxy; and b is an integer from0 to 2 and (ii) one or more condensable silicon monomers; wherein thecondensate and/or hydrolyzate further comprises as polymerized units oneor more second unsaturated monomers free of a condensablesilicon-containing moiety, wherein at least one second unsaturatedmonomer has the formula

wherein Z is chosen from an acid decomposable group, a C₄₋₃₀ organicresidue bound to the oxygen through a tertiary carbon, a C₄₋₃₀ organicresidue comprising an acetal functional group, and a monovalent organicresidue having a lactone moiety; and R¹⁰ is independently chosen from H,C₁₋₄ alkyl, C₁₋₄ haloalkyl, halogen, and CN, and (c) one or morecrosslinkers free of Si—O linkages.
 2. The composition of claim 1wherein at least one condensable silicon monomer has the formula (8)Si(R⁵⁰)_(p)(X)_(4-p)  (8) wherein p is an integer from 0 to 3; each R⁵⁰is independently chosen from a C₁₋₃₀ hydrocarbyl moiety and asubstituted C₁₋₃₀ hydrocarbyl moiety; and each X is independently chosenfrom halogen, C₁₋₁₀ alkoxy, —OH, —O—C(O)—R⁵⁰, and (O—Si(R⁵¹)₂)_(p2)—X¹;X¹ is independently chosen from halogen, C₁₋₁₀ alkoxy, —OH, and—O—C(O)—R⁵⁰; each R⁵¹ is independently chosen from R⁵⁰ and X; and p2 isan integer from 1 to
 10. 3. The composition of claim 2 wherein p=0 or 1.4. The composition of claim 1 wherein L is a divalent linking group. 5.The composition of claim 4 wherein the divalent linking group is anorganic radical having from 1 to 20 carbon atoms and optionally one ormore heteroatoms.
 6. The composition of claim 4 wherein the divalentlinking group has the formula —C(═O)—O-L¹- wherein L¹ is a single bondor an organic radical having from 1 to 20 carbon atoms.
 7. Thecomposition of claim 1 wherein at least one second unsaturated monomerhas an acidic proton and having a pKa in water from −5 to
 13. 8. Thecomposition of claim 1 wherein the condensate and/or hydrolyzate furthercomprises as polymerized units one or more unsaturated monomers having achromophore moiety.
 9. The composition of claim 8 wherein thechromophore moiety is pendent from the polymer backbone.
 10. A methodcomprising (a) coating a substrate with the composition of claim 1 toform a coating layer; (b) curing the coating layer to form a polymericunderlayer; (c) disposing a layer of a photoresist on the polymericunderlayer; (d) pattern-wise exposing the photoresist layer to form alatent image; (e) developing the latent image to form a patternedphotoresist layer having a relief image therein; (f) transferring therelief image to the substrate; and (g) removing the polymeric underlayerby wet stripping.
 11. The method of claim 10 wherein at least onecondensable silicon monomer has the formula (8)Si(R⁵⁰)_(p)(X)_(4-p)  (8) wherein p is an integer from 0 to 3; each R⁵⁰is independently chosen from a C₁₋₃₀ hydrocarbyl moiety and asubstituted C₁₋₃₀ hydrocarbyl moiety; and each X is independently chosenfrom halogen, C₁₋₁₀ alkoxy, —OH, —O—C(O)—R⁵⁰, and (O—Si(R⁵¹)₂)_(p2)—X¹;X¹ is independently chosen from halogen, C₁₋₁₀ alkoxy, —OH, and—O—C(O)—R⁵⁰; each R⁵¹ is independently chosen from R⁵⁰ and X; and p2 isan integer from 1 to
 10. 12. The method of claim 10 wherein L is adivalent linking group having the formula —C(═O)—O-L¹- wherein L¹ is asingle bond or an organic radical having from 1 to 20 carbon atoms. 13.The method of claim 10 wherein the condensate and/or hydrolyzate furthercomprises as polymerized units one or more unsaturated monomers having achromophore moiety.